Azides

ABSTRACT

Disclosed are azides of the formula   WHEREIN R is a polyvalent organic radical, and n and m are each 1-10. They are useful for bonding receptive polymers to ethylenically unsaturated hydrocarbon silane treated glass and, particularly when m 1, for linking together the polymer chains of receptive polymers. Because in the reaction of these compounds with receptive polymers the azidoformate radicals react substantially faster than the azidosulfonyl radicals, linking of receptive polymers with these compounds can be effected in two steps. (1) After forming a blend of receptive polymer and azide of the formula, establishing and maintaining the blend in a temperature range for a period of time selected to permit at least a substantial portion of the azidoformate radicals to react with the polymer with a minimum of the azidosulfonyl radicals having reacted with the polymer, whereby a substantially nonlinked, but reacted, polymer (ankylomeric polymer) is formed, and (2) establishing and maintaining the ankylomeric polymer in a temperature range for a period of time selected to permit at least a substantial portion of the azidosulfonyl radicals to react with the ankylomeric polymer, whereby linking of the polymer chains takes place.

United States Patent [191 Breslow 1 1 3,859,261 1 Jan. 7, 1975 i 1AZIDES [75] Inventor: David S. Breslow, Wilmington, Del.

[22] Filed: Dec. 20, 1972 [21] Appl. N0.': 317,014

Related US. Application Data [60] Division of Ser. No. 151,157, June 8,1971, Pat. No. 3,766,216, which is a continuation-in-part of Ser. No.761,847, Sept. 23, 1968, abandoned.

[56] References Cited UNITED STATES PATENTS 3,058,944 10/1962 Breslow260/41 3,284,421 ll/l966 Breslow 260/80.77 3,583,939 6/1971 Bostick260/46.S

Primary Examiner-Christopher A. Henderson Attorney, Agent, orFirm-Marion C. Staves [57] ABSTRACT Disclosed are azides of the formulawherein R is a polyvalent organic radical, and n and m are each l-l0.They are useful for bonding receptive polymers to ethylenicallyunsaturated hydrocarbon silane treated glass and, particularly when m l,for linking together the polymer chains of receptive polymers. Becausein the reaction of these compounds with receptive polymers theazidoformate radicals react substantially faster than the azidosulfonylradicals, linking of receptive polymers with these compounds can beeffected in two steps. (1 After forming a blend of receptive polymer andazide of the formula, establishing and maintaining the blend in atemperature range for a period of time selected to permit at least asubstantial portion of the azidoformate radicals to react with thepolymer with a minimum of the azidosulfonyl radicals having reacted withthe polymer, whereby a substantially nonlinked, but reacted, polymer(ankylomeric polymer) is formed, and (2) establishing and maintainingthe ankylomeric polymer in a temperature range for a period of timeselected to permit at least a substantial portion of the azidosulfonylradicals to react with the ankylomeric polymer, whereby linking of thepolymer chains takes place.

7 Claims, No Drawings AZIDES This application is a division of mycopending US. application Ser. No. 151,157, filed June 8, 1971, now US.Pat. No. 3,766,216, which is in turn a continuation-in-part ofapplication Ser. No 761,847, filed Sept. 23, 1968, and now abandoned.

This invention comprises a new class of azide compounds and their use inlinking polymers. Each member of the class is an organic compoundcharacterized by at least one azidoformate radical and by at least oneazidosulfonyl radical. The compounds of this class are represented bythe generic formula:

mgysroimy wherein R is a polyvalent organic radical, containing at leastone carbon atom per azido group, each azido group being attached to adifferent carbon atom in said R group, and n and m are integers,generally each being l-l0, and preferably each being l-2. Generally, Ris selected from the group consisting of the saturated and unsaturated,aliphatic, cycloaliphatic and aromatic hydrocarbon,hydrocarbon-xy-hydrocarbon, and hydrocarbon-sulfonyl-hydrocarbonpolyvalent radicals and the corresponding halo-substituted radicals. Inpreferred embodiments of this invention R is an organic radical selectedfrom the group consisting of radicals derived by the removal of two ormore hydrogen atoms from alkanes such as, for example, the straight andbranched C -C most preferably C -C2). alkanes which include, forinstance, ethane, propane, butane, isobutane, pentane and its isomers,hexane and its isomers, octane and its isomers, decane and its isomers,dodecane and its isomers, octadecane and its isomers, and the like;cycloalkanes such as, for example, the C C100, most preferably C -Ccycloalkanes which include, for instance, cyclopropane, cyclobutane,cyclopentane, cyclohexane, cyclooctane, and the like; alkyl-cycloalkanessuch as, for example, the C -C alkyl- (C -C cycloalkanes which include,for instance, ethylcyclohexane, methylcyclobutane, and the like; arenessuch as benzene, naphthalene, diphenyl, and the like; alkyl substitutedarenes such as, for example, the C -C most preferably C C alkylsubstituted arenes whcih include, for instance, toluene, ethylbenzene,0-, mand p-xylene, o-, m-, and p-diethylbenzene, and the like;alkylene-diarenes such as, for example, the C C most preferably C -Calkylene-diarenes which include, for instance, diphenylmethane, 1,2-diphenylethane, 1,1-diphenylpropane, 1,3- diphenylpropane,2,2-diphenylpropane, and the like; dialkylcycloalkanes such as, forexample, the di- (C -C alkyl-(C -C cycloalkanes which include, forinstance, 1,2-, 1,3-, and 1,4-dimethylcyclohexane, 1,2- and1,3-dimethylcyclopentane, and the like; and the alkyloxyalkane,aryloxyarene, alkaryloxyarene, alkaryloxyalkarene, aralkyloxyalkane,aralkyloxyaralkane, alkyloxyalkarene, and the like compounds as well asthe corresponding sulfonyl compounds specific examples of which includediethyl ether, propyl butyl ether, diphenyl ether, oxy-bis(p-methylbenzene), oxybis(phenyl methane), butyl sulfonyl butane, and the likecompounds; and the foregoing compounds with fluoro, chloro, bromo andiodo substituents. When an azide of this invention is to be used as alinking agent for polymers, R preferably is substantially inert in thelinking reactions.

Exemplary of the new azide compounds of this invention are thosecompounds having the foregoing generic formula wherein:'

l. R is an aliphatic radical:

l-azidosulfonyl ethane-Z-azidoformate l-azidosulfonylpropane-3-azidoformate l-azidosulfonyl butane-4-azidoformatel-azidosulfonyl butane-3-azidoformate 2-azidosulfonylbutane-B-azidoformate 1-azidosulfonyl-2,2-dimethyl ethane-Z-azidoformatel-azidosulfonyl-3-methyl propane-3-azidoformate l-azidosulfonyl-Z-methylpropane-3-azidoformate l-azidosulfonyl pentane-S-azidoformatel-azidosulfonyl pentane-4-azidoformate l-azidosulfonylpentane-3-azidoformate l-azidosulfonyl pentane-Z-azidoformate4-azidosulfonyl pentane-5-azidoformate 2-azidosulfonylpentane-S-azidoformate l-azidosulfonyl-Z-methyl butane-Z-azidoformatel-azidosulfonyl-Z-methyl butane3-azidoformate l-azidosulfonyl-2-methylbutane-Lazidoformate 2-azidosulfonyl-2-methyl butane-B-azidoformate2-azidosulfonyl-2-methyl butane-4-azidoformatel-azidosulfonyl-2,2-dimethyl propane-3- azidoformate l-azidosulfonylhexane-6-azidoformate l-azidosulfonyl hexane-S-azidoformate2-azidosulfonyl hexane-6-azidoformate 2-azidosulfonylhexane-4-azidoformate 2-azidosulfonyl hexane-S-azidoformate3-azidosulfonyl hexane-4-azidoformate 1-azidosulfonyl-6-azidoformatehexene-Z l-azidosulfonyl-2-methyl pentane-Z-azidoformatel-azidosulfonyl-Z-methyl pentane-3-azidoformate 2-methyl-3-azidosulfonylpentane-S-azidoformate 2-azidosulfonyl-2-methyl pentane-S-azidoformate4-azidosulfonyl-4-methyl pentane-5-azidoformate 2-azidosulfonyl-2-methylpentane-4-azidoformate l-azidosulfonyl-4-m'ethyl pentane-4-azidoformate2-azidosulfonyl-3-methyl pentane-4-azidoformate1-azidosulfonyl-2,Z-dimethyl butane-3-azidoformatel-azidosulf0nyl-2,Z-dimethyl butane-4-azidoformatel-azidosulfonyl-3,3-dimethyl butane-4-azidoformate2,2-dimethyl-3-azidosulfonyl butane-4-azidoformatel-azidosulfonyl-2,S-dimethyl butane-2-azidoformate2-azidosulfonyl-2,3-dimethyl butane-3-azidoformate l-azidosulfonylheptane-7-azidoformate 2-azidosulfonyl-3-methyl hexane-4-azidoformate2-azidosulfonyl-2-methyl hexane-6-azidoformate l-azidosulfonyl-3methylhexane-6-azidoformate 2-methyl-4-azidosulfonyl hexane-6-azidoformatel-azidosulfonyl-4-methyl hexaneQ-azidoformatel-azidosulfonyl-2,Z-dimethyl pentane-3- azidoformate2-azidosulfonyl-4,4-dimethyl pentane-S- azidoformatel-azidosulfony]-2,2-dimethyl pentane-S- azidoformatel-azidosulfonyl-2,4-dimethyl pentane-3- azidoformate2-azidosulfonyl-2,4-dimethyl pentane-3- azidoformate2-azidosulfonyl-2,4-dimethyl azidoformate l-azidosulfonyloctane-8-azidoformate 4-azidosulfonyl octane-S-azidoformate2-azidosulfonyl-2-methyl heptane-6-azidoformate 2-azidosulfonyl-3-methylheptane-4-azidoformate 3-azidosulfonyl-4-methyl heptane-4-azidoformate3-azidosulfonyl-4-methyl heptane-S-azidoformatel-azidsulf0nyl-2,5-dimethyl hexane-Z-azidoformate2-azidosulfonyl-2,5-dimethyl hexane-S-azidoformate3-azidosulfonyl-3,4-dimethyl hexane-4-azidoformate pentane-4-l-azidosulfonyi decane-lOazidoformate l-azidosulfonyldecane-Z-azidoformate 1-azid0sulf0nyl-2-methyl nonane-2-azidoformate3-azidosulfonyl-2,6-dimethy] 'octane-8-azidoformate2-azid0sulf0nyl-3,7-dimethyl octane-S-azidoformate4-azidosulfonyl-2,7-dimethyl octane-S-azidoformate4-azidosulfonyl-4,S-dimethyl octane-S-azidoformate 3-azidosulfonyl-2,2,5,S-tetramethyl hexane-4- azidoformate 3-azid0sulfonyl-2,3 ,4,5-tetramethyl hexane-4- azidoformate 2-azidosulfonylundecane-B-azidoformate 9-azidosulfonyl undecane-l O-azidoformate1-azidosulfony1-2-methyl decane-Z-azidoformate2-azid0sulfonyl-2,6-dimethyl nonane-8-azidoformateZ-azidosulfonyl-Z,S-dimethyl nonane-8-azidoforamte2-azidosulfonyl-3,7-dimethyl n0nane-8-azidoformate3-azid0sulf0nyl-3-methyl6-ethyl octane-6- azidoformatel-azidosulfonyl-2-methyl-S-isobutyl azidoformate 6-azidosulfonyldodecane-7-azidoformate l-azidosulfonyl-2-methyl undecane-Z-azidoformate3-azidosulfonyl-3,6-dieth'yl octane-6-azidoformate4-azidosulfonyl-4,5-diethyl octane-S-azidoformate hexane-6-4-azidosulfonyl-2,4,5,7-tetramethy1 octane-5- azidoformate3-azidosulfonyl-2,2,3,4,5,5-hexamethyl hexane-4- azidoformatel-azid0sulfonyl-2-is0amyl-5-methyl hexane-2- azidoformatel-azidosulfonyl-Z-methyl dodecane-Z-azidoformate5-azid0sulfonyl-2,5,6,9-tetramethyl decane-6- azidoformate4-azidosulfonyl-4,S-dipropyl octane-S-azidoformate l-azidosulfonylhexadecane-lfi-azidoformate l-azidosulfonyl hexadecane-2-azidoformatel-azidosulfonyl hexadecane-l l-azidoformate 6-azidosulfonyl-2,6,7,ll-tetramethyl dodecane-7- azidoformate 4-azidosulfonyl-4,9-dipr0pylazidoformate l-azidosulfonyl octadecane- 1 8-azidoformatel-azidosulfonyl nonadecane-l9-azidoformate1-azidosulfonyleicosane-20-azid0f0rmate 5 -aZidosulf0nyl-8-isoamyl-2,5,1 l-

trimethyldodecane-8-azid0formate l-azidosulfonylheneicosane-Z l-azidoformate 1-azidosulfonyldocosane-22-azidoformate 11-azidosulf0nyldocosane-12-azidoformate lO-azidosulf0nyl-l0,ll-dimethyleicosane-l lazidoformatel2-azidosulfonyltetracosane-13-azidoformate l l-azidosulfonyl-l l,12,-dimethyldocosane-l2- azidoformate 1-azid0sulf0nyl-4,8, l 3,17-tetramethyleicosane-20- azidoformatel-azid0sulfonylpentacosane-ZS-azidoformate S-azidosulfonyl-S,l4-dibutyloctadecane-14- azidoformate 14-azidosulfonyloctacosanel5-azid0f0rmate 1-azidosulf0nyld0triacontane-3 2-azid0formatel-azid0sulfonyltetratriacontane- 1 S-azidoformate7-azidosulfonyl-7,16-dihexyldocosane-l6- azidoformate18-azidosulfonylhexatriacontane-19-azidoformatel,2-bis(azidosulfonyl)propane-3-azidoformatel,3-bis(azidosulf0nyl)propane-Z-azidoformate2-azidosulf0nylpr0pane-1,3-bis(azidoformate)l-azid0sulfonylbutane-2,3-bis(azidoform ate) l-azidosulfonylbutane-Z,4-bis(azidoform ate) 2-azidosulfonylbutane-l ,3-bis(azidof0rmate)l,2-bis(azidosu'lfonyl )butane-3-azidoformatel,2-bis(azid0sulfonyl)pentane-3-azidoformate1,3-bis(azidosulfonyl)pentane-Z-azidoformatel-azidosulfonylpentane-2,3-bis( azidoformate)l-azidosulfonylpentane-2,4-bis(azidoformate)1,2-bis(azidosulfonyl)pentane-4-azidoformate2-azid0s1ilfonylpentane-3,4-bis(azidoformate)1,2-bis(azidosulfonyl)-2-methylbutane-3- azidoformatel-azid0sulfonylhexane-2,5-bis(azidoformate) 2,3-bis(azidosulfonyl)hexane-4-azidof0rmate l,2-bis(azidosulfonyl )-2-methylpentane-3-azidoformate 1,4-bis(azidosulfonyl)heptane-7-azidoformatel,7-bis(azidosulfonyl)heptane-4-azidof0rmatel-azidosulfonylheptane-4,7-bis( azidoformate) 2-methyl-3 ,5-bis(azidosulf0ny1)hexane-6- azidoformate2-methyl-4-azid0sulf0nylheptane-6,7-

bis(azidof0rmate) 3,5-bis(azidosulfonyl)-3-ethylhexane-6-azidoformate3-azid0sulfonyl-2,3-dimethylhexane-5 ,6-

bis(azidoformate) 5-azidosulfonyl-5-methyloctane-7,8-

bis(azidoformate) l,2-bis(azidosulfonyl)decane-4-azidoformate3,6-bis(azidosulf0nyl)decane-l0-azidoformatel,2-bis(azidosulfonyl)-4-propylheptane-4- azidoformate1-azidosulfonyl-4-methyldecane-Z,4-

bis( azidoformate) 2,3-bis(azidosulfonyl)-2,6-dimethyloctane-8-azidoformate l-azidosu1fonylundecane-5 ,6-bis(azidoformate) dodecane-9-l-azidosulfonyl-Z-chlorophenyl-4-azidoformatel-azidosulfonyl-2-fluorophenyl-4-azidoformatel-azidosulfonyl-2-bromophenyl-4-azidoformatel-azidosulfonyl-2-iodophenyl-4-azidoformate l-azidosulfonyl-3-chlorophenyl-4-azidoformatel-azidsulfonyl-2-chlorophenyl-3-azidoformatel-azidosulfonyl-4-chlorophenyl-3 -azidoformate l-azidosulfonyl-S-chlorophenyl- -azidoformatel-azidosulfonyl-3-chlorophenyl-Z-azidoformatel-azidosulfonyl-4-chlorophenyl-2-a2idoformate1-azidosulfonyl-2,5-dichlorophenyl-4-azidoformate l-azidosulfonyl-3 ,5-dichlorophenyl-4-azidoform ate l-azidosulfonyl-3 ,5-dibromophenyl-4-azidoform ate l-azidosulfonyl-3,5-diiodophenyl-4-azidoformate l-azidosulfonyl-3 ,5-difluorophenyl-4-azidoformate l-azidosulfonyl-2,3 ,5-trichlorophenyl-4-azidoformate 1-azidosulfonyl-2,4,5-trichlorophenyl-3- azidoformate1-azidosulfonyl-3,4,5-trichlorophenyl-2- azidoformate l-azidosulfonyl-Z,3 ,5 ,6-tetrachlorophenyl-4- azidoformate l,3-bis(azidosulfonyl)-2,4,6-trichlorophenyl-5- azidoformate l,2-bis(azidosulfonyl)-3-chlorophenyl-4,5-

bis( azidoformate) l-azidosulfonyl-4-chloronaphthalene-2-azidoformatel-azidosulfonyl-4-bromonaphthalene-2- azidoformate l,2-bis(azidosulfonyl)-6-chloronaphthalene-3- azidoformate l,2-bis(azidosulfonyl)-6-chloronaphthalene-3 ,4-

bis(azidoformate) 4-azidosulfonyl-2,2 '-dichlorodiphenyl-4 azidoformatev 4-azidosulfonyl-2,2,5,5,6,6-hexachlorodiphenyl- 4'-azidoformate3-azidosulfonyl-2,2'-dichlorooxydipropyl-3'- azidoformate4-azidosulfonyl-2,2-dibromooxydibutyl-4- azidoformate4-azidosulfonyl-2,2 ,5 ,5

tetrachlorooxydicyclohexane-4-azidoformate4-azidosulfonyl-2,2-dichlorooxydiphenyl-4'- azidoformate4-azidosulfonyl-2,2'-dibromooxydiphenyl-4'- azidoformate3-azidosulfonyl-5 ,5 '-dichlorooxydiphenyl-3 azidoformate 3,3 '-bis(azidosulfonyl)-5 ,5 '-dichlorooxydiphenyl- 4,4-bis(azidoformatel-(4-azidosulfonyl-2'-chlorobutylsulfonyl)-2-chlorobutane-4-azidoformate1-(4'-azidosulfonyl-3'-chlorocyclohexylsulfonyl)-3-chlorocyclohexane-4-azidoformate l-(4'-azidosulfon-yl-3 ,5'-dichlorophenylsulfonyl)- 3,5-dichlorophenyl-4-azidoformate The azidesof this invention in general range from normally liquid to solid at2025C. and at atmospheric pressure. They have characteristic infraredspectra, each containing the strong azide band at 2100-2200 cm.', astrong carbonyl band at about 1740 cm. and sulfonyl bands at about 1370cm. and l 170 emf. When heat is applied to the compounds of thisinvention, they decompose, giving off nitrogen. As

the temperature increases, the overall decomposition rate increases. Atany given temperature the azidoformate radicals of these compoundsdecompose at a faster rate than the azidosulfonyl radicals. In general,the decomposition rate of the azidoformate portion of each compound ofthis invention is about the same at about C. as the decomposition rateof the azidosulfonyl portion at about C. The azidoformate andazidosulfonyl radicals of the compounds of this invention are veryreactive. They readily combine with ethylenically unsaturatedhydrocarbon groups in a variety of compounds, including unsaturatedhydrocarbon containing silanes. They react with receptive polymers andcombine therewith. In so doing, however, the azidoformate portion of thecompound in each case has a faster reaction rate than the azidosulfonylportion at the same temperature. Indeed, in reacting with receptivepolymers and the like, the azidoformate portion of the compound in eachcase has about the same reaction rate at about 130C. as theazidosulfonyl portion of the compound at about 170C.

Each of the azide compounds of this invention is made by reacting thecorresponding halosulfonylchloroformate compound with alkali metalazide. This is done by admixing the halosulfonylchloroformate compoundwith one or more alkali metal azides, preferably in a normally liquidmedium, in a temperature range of 0100C. and at ambient atmosphericpressure. Examples of alkali metal azides include sodium azide, lithiumazide, potassium azide, and the like. Examples of a normally liquidmedium include acetone, acetone-water, ethanol, ethanol-water,chlorinated hydrocarbon (for instance, methylene chloride, chloroform,1,1,2-trichloroethane, and the like, including mixtures of specificchlorinated hydrocarbons)-water, hydrocarbon (for instance, benzene,toluene, xylene and the like, including mixtures of specifichydrocarbons)-water, and the like.

The corresponding halosulfonyl-haloformate compound is made in a numberof ways.

One way is by the halosulfonation of the corresponding haloformate. Whenthe corresponding haloformate is an alkyl or cycloalkyl haloformate, thehalosulfonation is performed by admixing the haloformate with eithersulfuryl halide or a mixture of halogen and sulfur dioxide gases and aperoxide as catalyst. In lieu of a catalyst or in addition to acatalyst, the mixture of reactants can be exposed to ultraviolet lightto effect reaction. Preferably the reaction is carried out in ahalogenated solvent such as, for example, methylene chloride, ethylenedichloride, chloroform, and the like, and the temperature range isgenerally from about 0 to about 80C. When the corresponding haloformateis an aryl haloformate or arylalkyl haloformate the halosulfonation ispreferably carried out by admixing the haloformate with halosulfonicacid in a temperature range from about 0 to about 75C. and preferably ina halogenated solvent like methylene chloride, chloroform, or the like.

The halosulfonation reaction of aliphatic and aromatic chloroformates togive corresponding halosulfonyl-haloformate compounds is an excellentway for introducing one or more halosulfonyl radicals into thesechloroformate compounds. However, the reaction product usually comprisesa random mixture of isomers. Moreover, in the halosulfonation reactionof aliphatic chloroformates, when the reaction of an aliphatichaloformate with sulfur dioxide and halogen 0c curs, some of the halogenis also introduced into the compound. This is just a normal halogenationof the alkyl chain. The extent of halogenation of the alkyl chain can bevaried, higher temperatures and only small excesses of sulfur dioxidefavoring higher halogen contents, but usually halogenation of the alkylchain cannot be completely eliminated. Halogenation of the alkyl chainis an advantage when it is desired to have a minimum number of sulfonylazide radicals in the compound, because halo groups and sulfonyl halidegroups deactivate adjacent carbon atoms to further substitution. Ingeneral, halo radicals in the aliphatic azides of this invention aresubstantially inert in polymer linking reactions.

Another way of making halosulfonyl-haloformate compounds is by effectingwith a catalyst such as dimethylformamide or the like, reaction of thealkali metal salt of the corresponding hydroxy organosulfonic acid withphosgene at about a 2:1 mole ratio at -60C. or with phosgene at about a1:1 mole ratio at 0-60C. followed by thionyl chloride'at about a 1:1mole ratio at 0-100C. Generally this is done by admixing the reactantsand the catalyst in a halogenated solvent like methylene chloride,chloroform or the like, or a hydrocarbon like benzene, toluene and thelike.

Another process for making compounds of this invention is by reacting(1) an organo compound containing one or more isocyanate radicals andeither one or more azidosulfonyl radicals, or one or more azidoformateradicals, with (2) an active hydrogen compound containing either one ormore azidoformate radicals or one or more azidosulfonyl radicals. Anactive hydrogen compound, well defined in the polyurethane art, has atleast one radical capable of combination reaction with the isocyanategroup. Examples of such a radical include the carboxylic acid radical,the amino radical, the hydroxy radical, and the like.

The azide compounds of this invention are useful for bonding receptivepolymers to ethylenically unsaturated hydrocarbon silane treated glass,and they can be used to like, that is, chain extend, bridge, andcrosslink, receptive polymers. ln linking receptive polymers, compoundsof this invention having more than one azidoformate radical per moleculecan be used. However, when the linking is performed sequentially (morefully described hereinafter), the compounds having only one azidoformateradical per molecule (in formula m l) are preferred because there isless chance for premature chain linking to occur. In this specification,receptive polymer means a polymer having, in each polymer chain, atleast one and generally more than one monomer unit (referred to as anazidoformate radical reactive monomer unit) capable of combinationreaction with an azidoformate radical of a compound of this invention,whereby the residue of the compound is chemically bonded to the polymer,or at least one and generally more than one monomer unit (referred to asan azidosulfonyl reactive monomer unit) capable of combination reactionwith an azidosulfonyl radical of any compound of this invention, wherebythe residue of the compound is chemically bonded to the polymer. Usuallya monomer unit that is capable of combination reaction with theazidoformate radical is capable of combination reaction with theazidosulfonyl radical, and vice versa. Nearly all polymers are receptivepolymers. Preferred examples of a receptive polymer include all types ofhydrocarbon polymers including saturated and unsaturated, linear andnon-linear crystalline and amorphous homopolymers, copolymers,terpolymers, and the like, for example, polyethylene, polypropylene,polystyrene, styrene-butadiene rubber, butyl rubber, natural rubber,polybutadiene, polyisobutylene, ethylene-propylene copolymer, cis-l,4-polyisoprene, ethylene-propylene-dicyclopentadiene terpolymer, and thelike, and blends of these polymers with each other and blends of thesepolymers with organic non-hydrocarbon polymers. In addition tohydrocarbon polymers, preferred examples of a receptive polymer includea large number of organic nonhydrocarbon polymers includinghomopolymers, c0- polymers, terpolymers, and the like. Typical of theseorganic non-hydrocarbon polymers are cellulose esters such as, forexample, cellulose acetate-butyrate, cellulose acetate-propionate,cellulose acetate, cellulose propionate, cellulose butyrate, and thelike; cellulose ethers such as, for example, hydroxyethyl cellulose,hydroxypropyl cellulose, and the like; polyesters such as poly(ethyleneglycol terephthalate), drying and nondrying alkyd resins and the like;poly(alkylene oxide) polymers such as poly(ethylene oxide),poly(propylene oxide), poly(ethylene oxide) (propylene oxide),polyamides such as nylon, and the like; allyl pentaerythritolderivatives such as, for example, the condensate of triallylpentaerythritol with diallylidene pentaerythritol, esters of triallylpentaerythritol and drying oil fatty acids, and the like; poly(vinylalkyl ethers) such as, for example, poly(vinyl methyl ether) and thelike; poly(vinyl acetals) such as, for example, poly(vinyl butyral) andthe like; vinyl chloride polymers having a vinyl chloride content of atleast ten mol percent, such as, for example, poly(vinyl chloride), vinylchloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloridecopolymers, vinyl chloride-maleic anhydride copolymers, vinylchloride-fumaric acid copolymers, vinyl chloridevinyl acetal copolymers,such as, for example, the vinyl chloride'vinyl butyral copolymers, vinylchloridevinylidene chloride-acrylonitrile terpolymers, vinylchloride-vinylacetate-maleic anhydride terpolymers, and the like;nitrocellulose; chlorinated natural rubber; sulfochlorinatedpolyethylene; polysulfide rubber; polyurethane rubber; poly(vinylacetate); ethylenevinyl acetate copolymer; poly(vinylidene chloride);vinylidene chlorideacrylonitrile copolymers; ethylacrylate-Z-chloroethyl vinyl ether copolymers; poly- (ethyl acrylate);poly(ethyl methacrylate); poly[3,3- bis(chloromethyl)oxetane];vinylmodified poly(dimethylsiloxane); polychloroprene;butadiene-acrylonitrile copolymers; and the like.

To use an azide compound of this invention as a chain extender, bridgingagent or cross-linking agent for a receptive polymer, at least one azidecompound is blended with at least one receptive polymer, and theresulting blend or mixture is then treated to effect reaction of theazidoformate and azidosulfonyl radicals, preferably on a sequentialbasis, with monomer units in the polymer material capable of linkgereaction with these radicals.

The concentration of the azide compound in the blend can vary over awide range, depending on whether chain extension, bridging orcross-linking is involved, and the extent to which each is desired inthe final product. Generally, however, the concentration will be in therange from about 0.01 to about 50% by weight of the receptive polymermaterial, and preferably in a range from about 0.1 to about by weight ofthe receptive polymer material. Higher and lower operableconcentrations, however, are within the broader concepts of thisinvention.

The blend of receptive polymer and azide compound is made byconventional ways and means. For example, it is made by milling on aconventional rubber mill in a temperature range at which the polymer issufficiently soft to permit dispersion in it of the azide compound. Itis made also by dissolving the azide compound in a solution of thereceptive polymer. Usually, the solvent is removed prior to subsequentheat treatment of the blend.

In addition to receptive polymer and azide com pound, the blend cancomprise other components such as, for example, one or more extenders,fillers, colorants including pigments and the like, plasticizers,stabilizers including antioxidants, ultraviolet light inhibitors,thermal stabilizers, and the like, anti-static agents, propertyimprovers, and the like/In preferred embodiments of this invention, totie'a maximum amount of azide compound to the receptive polymer with aminimum of polymer degradation and without premature linking together ofpolymer chains, a component, which can be referred to as a radical trap,is used. This radical trap consists essentially of at least onecompound, in some embodiments two or more compounds, that inhibits freeradical type reactions. Examples of such a compound includenitrobenzene, dinitrobenzene, 4,4'-thiobis(6 t-butyl-m-cresol), sulfur,2,6-di-t-butyl-p-cresol, quinone, hydroquinone, phenylnapthylamine, andthe like. The amount of the radical trap compound used can vary over awide range. However, in general it is in a range from about l% by weightto about 5 times the weight of the azide compound and preferably in arange from about to about 100% by weight of the azide compound.

Treatment of the blend to effect linkage reaction between the azidecompound and the receptive polymer material is by heat, by irradiation,or by both heat and irradiation.

In one general embodiment the blend with or without irradiation isestablished and maintained in a temperature range for a period of timeselected to effect linkage reaction of a substantial portion of all ofthe azidoformate and azidosulfonyl radicals with the polymer material.

However, in another general embodiment this is done sequentially in twosteps.

In the first step the blend with or without irradiation is establishedand maintained in a temperature range for a period of time selected toeffect reaction of at least a substantial portion of the azidoformateradicals with the azidoformate radical receptive monomer units, withonly a minimum, if at all, of the azidosulfonyl radicals undergoingreaction with azidosulfonyl radical receptive monomer units. The resultis a modified but substantially unlinked polymer product that hasapproximately the same processability properties as the receptivepolymer before reaction with the azidoformate radicals. Receptivemonomer units present in the polymer chains are chemically bondedthrough reacted azidoformate radicals to azide compounds. Theazidosulfonyl radicals are substantially unreacted, wherefore, thesemodified polymers have unreacted azidosulfonyl radicals. Each polymerthus modified has substantially the same processability properties asthe unmodified receptive polymer, but now is capable of being linked bymerely applying heat, irradiation, or both heat and irradiation to it toeffect combination reaction between azidosulfonyl radical receptivemonomer units and azidosulfonyl radicals. Such a polymer is termedherein an ankylomeric polymer".

In the second step of this sequential general embodiment the ankylomericpolymer product with or without irradiation is established andmaintained in a temperature range for a period of time selected toeffect combination reaction of at least a substantial portion of theazidosulfonyl radicals with azidosulfonyl receptive monomer units andthereby link together a substantial portion of the ankylomeric polymerchains.

In one practice of the sequential embodiment the second step isperformed right after the first step.

In another practice of the sequential embodiment the ankylomeric polymerproduct generally, but not necessarily, in the form of flakes, pelletsor sheets, is cooled to 2025C., and later, when desired, subjected tothe second step. The ankylomeric polymer product, when cooled to20-25C., can be stored and transported in bulk, or in containers such asbags, drums or the like, without substantial migration of linkagematerial to the surface of the polymer product and without substantialloss of linkage material by evaporation. The ankylomeric polymer producthasfurther advantages in that it can be made on a large scale by thepolymer producer, thereby permitting a more uniform product to be made,and then shipped in smaller quantitiesto the converter or fabricator,who may be limited in processing equipment and processing capacity, whoperforms the second step in making useful articles from it. In thisconnection the second step can be performed in preparing and applyingcoatings of the ankylomeric polymer product to wire, webs, slieets,shaped articles, and the like, in extruding the ankylomeric polymerproduct into articles such as, for example, pipes, rods, sheets, and thelike, and in molding the ankylomeric polymer product into usefularticles.

The best mode now contemplated for carrying out this invention isillustrated by the following examples of various aspects and specificembodiments of this invention. This invention is not limited to thesespecific embodiments. In the examples, all parts and percentages are byweight unless otherwise specified.

EXAMPLE 1 ylformamide (2.8 parts) is admixed with the reaction mixtureand then phosgene is bubbled slowly through the mixture for 2 hours.After standing for 16 hours at 2025C., the reaction mixture, typically alight yellow slurry, is sparged with nitrogen and then stripped ofvolatiles under aspirator vacuum. The remaining portion of the reactionmixture is with methylene chloride and centrifuged to remove the solids.The resulting solution is subjected to evaporation to remove themethylene chloride. The residue typically is an orange oil (42 parts).It consists essentially chlorosulfonylpropyl-3-chloroformate.

A portion (30 parts) of this oil is dissolved in methylene chloride (200parts) and the resulting solution is admixed with a slurry of sodiumazide (35.4 parts), water (70 parts) and acetone (79 parts). The mixturethus formed is stirred for 20 hours at 2025C. Water (100 parts) is thenadmixed with the reaction mixture and after phase separation has takenplace, the waterimmiscible phase is separated from the aqueous phase,washed with water, dried over sodium sulfate, and then subjected tovacuum to remove substantially all of the methylene chloride. Theproduct that remains is typically a yellow oil (28 parts). It consistsessentially of lazidosulfonylpropyl-3-azidoformate.

A typical infrared spectrum of this product displays a strong carbonylpeak at 1745 emf, an azide peak at 2140 emf, and sulfonyl peaks at 1375cm." and 1170 cmf.

A typical elemental analysis of the material is as follows:

This product is useful as a cross-linking agent for polyethylene and thelike.

EXAMPLE 2 This example illustrates a process for making a productcomprising an azidosulfonylhexyl azidoformate isomer mixture.

A soltuion of n-hexyl chloroformate (280 parts), prepared from l-hexanoland phosgene, and methylene chloride (4000 parts) is cooled to 5C.Sulfur dioxide is then bubbled into this solution at the rate of 31parts per hour. Fifteen minutes after commencement of the introductionof sulfur dioxide gas into the solution, the solution is exposed toutra-violet light and chlorine gas is also bubbled through the solutionat the rate of 17.2 parts per hour. After seven hours, introduction ofboth gases is stopped, but the solution is left exposed to ultra-violetlight for an additional hour. The solution, which typically is colorlessat this stage, is warmed to 20-25C. It is then stripped by aspiratorvacuum of residual unreacted gases and of methylene chloride while itstemperature is raised to about 70C. While maintaining its temperature atabout 70C., the mixture remaining is subjected for one-half to a vacuumof about 0.7 millimeter of mercury. Following this step, the remainingmixture is subjected to distillation to remove therefrom unreactedn-hexyl chloroformate. The residue is typically a dark amber oil (347parts) consisting essentially of chlorosulfonylhexyl chloroformateisomers.

A portion (263 parts) of this oil is dissolved in meth ylene chloride(1000 parts) and the resulting solution is added dropwise to a slurry ofsodium azide (260 parts), water (250 parts) and acetone (200 parts). Theresulting mixture is stirred at 20-25C. for hours and then refluxed at48C. for 5 hours. The reaction mixture thus obtained is washed withwater and dried over sodium sulphate. The result is typically an ambercolored solution. Activated carbon black is admixed with the solutionand then removed by filtration. The

N S Cl Analyzed 27.4, 27.7 11.1 4.2 Calculated 30.4 11.6 0

This product is useful as a cross-linking agent for polypropylene andthe like.

EXAMPLE 3 This example illustrates 1-(3-azidosulfonylpropoxy)-butyl-4-azidoformate, and its synthesis.

Sodium (11.5 parts) is gradually added to 1,4- butanediol (180 parts)established and maintained at 100C. by heating. The temperature of theresulting solution is permitted to fall to C. and, while maintaining thesolution at this temperature, propanesultone (61 parts) is admixeddropwise with it. Typically a white solid precipitates and the reactionmixture becomes quite pastry. Consequently, tetrahydrofuran (220 parts)is added to make the reaction mixture more readily stirrable. Thetemperature of the thus diluted reaction mixture is established andmaintained for 4 hours at 65C. The reaction mixture is then slurriedwith acetone and filtered. The filter cake, typically a white solidmaterial, is washed with acetone several times, and then the solventportion is removed at 60C. under vacuum. The material that remains istypically a white powdery solid parts). It consists essentially of thesodium salt of 3-( hydroxybutoxy )-propylsulfonic acid.

A portion (82 parts) of this product is gradually added to a solution,established and maintained at -5C., of phosgene (104 parts) in methylenechloride (345 parts) and dimethylformamide (4.7 parts). The resultingreaction mixture is typically a cream colored slurry. After stirring theslurry for 20 hours at 3C., and then for 4 hours at 23C., volatilesubstances are removed under aspirator vacuum. The portion of thereaction mixture that remains is typically a grey colored slurry.

To this slurry are added thionyl chloride parts) and dimethylformamide(2.8 parts), and the resulting reaction mixture is stirred at 2025C. for64 hours. Volatiles are removed by vacuum from the reaction mixture andthe slurry that results is diluted with methylene chloride and filtered.The filtrate is subjected to vacuum to remove substantially all of themethylene chloride. The residue is typically an amber oil (86 parts). Itconsists essentially of 1-( 3-chlorosulfonylpropoxy)-butyl-4-chloroformate.

A portion (75 parts) of this oil is dissolved in acetone parts) and theresulting solution rapidly stirred while a slurry of sodium azide (66parts), water (100 parts) and acetone (80 parts) is admixed with it. Thereaction mixture which results is stirred for 20 hours at 2025C., andthen refluxed at 51C. for 3 hours. The reaction mixture is then admixedwith water (400 parts) and methylene chloride (135 parts). Phaseseparation occurs. The non-aqueous phase is separated from the aqueousphase, water washed, dried over sodium sulfate, and then subjected tovacuum to remove therefrom substantially all of the methylene chloride.The residue comprises a typically light amber oil (66 parts). Itconsists essentially of l-(3-azidosulfonylpropoxy)-butyl-4-azidoformate.

A typical infrared spectrum of this product has a strong azide peak at2135 cm., a carbonyl peak at 1735 cmf, as well as sulfonyl-peaks at 1375emf, and 1165 cmf.

A typical elemental analysis of this product is:

Analyzed 23.9, 24.2 12.2 Calculated 27.5 10.5

This product has utility as a cross-linking agent for polyethers such aspoly(ethylene oxide) and the like.

EXAMPLE 4 methylene chloride (1000 parts) is cooled at 5C. while passingin sulfur dioxide gas at the rate of 9.6 parts per hour. After aboutminutes the reaction mixture is exposed to ultraviolet light, andchlorine gas is introduced into the reaction mixture at the rate of 5.3parts per hour. Both chlorine and sulfur dioxide are continuously addedfor 4 hours to the reaction mixture, and then their addition is stopped.The methylene chloride is removed by high vacuum from the reactionmixture, giving an isomeric mixture of chlorosulfonyl cyclohexylchloroformate isomers. A typical yield of the mixture is 51 parts.

A portion (46 parts) of the chlorosulfonylcyclohexyl chloroformateisomer mixture is dissolved in methylene chloride (1000 parts) and addedto a slurry of sodium azide (39 parts) in water (75 parts) and acetone(100 parts). The mixture thus formed is stirred rapidly and refluxed for8 hours. It is then cooled to 25C. The resulting water-immiscible phaseis removed from the aqueous phase, washed with water, dried, and thensubjected to vacuum to remove the methylene chloride. The residue, thedesired product, consists essentially ofl-azidosulfonylcyclohexyl-4-azidoformate and isomers of this compound.

A typical elemental analysis of this product is as follows:

Calculated This product is useful as a cross-linking agent forpolypropylene.

EXAMPLE 5 This example illustrates a process for making a productcomprising a poly(azidosulfonyl)-chlorooctadecyl 5 azidoformate.

A solution of n-octadecyl chloroformate (166 parts), 0.5 mole preparedfrom n-octadecanol and phosgene) in methylene chloride (2000 parts) iscooled to 5C. Sulfur dioxide gas is then bubbled through the solution atthe rate of 72 parts per hour. After 15 minutes chlorine gas isintroduced into the reaction mixture at the rate of 39 parts per hour,and the reaction mixture is exposed to ultraviolet light. After 8 hoursof reaction with both chlorine and sulfur dioxide bubbling into thereaction mixture, the addition of both gases is stopped, and theexposure of the reaction mixture to ultraviolet light is continued foran additional hour. The resulting reaction mixture, a colorlesssolution, is warmed to 20-25C. and stripped by vacuum of methylenechloride. The residue is typically a viscous oil (320 parts).

A portion (166 parts) of this oil is dissolved in methylene chloride(1000 parts) and added to a slurry of sodium azide (130 parts, 2 moles),acetone (400 parts) and water (250 parts). After stirring the resultingmixture for 20 hours at 2025C., refluxing for 4 hours and cooling to2025C., the resulting water immiscible phase of the cooled reactionmixture is separated from the aqueous phase, water washed, dried andthen stripped of methylene chloride to give the desired product,typically an amber oil (167 parts). This product consists essentially ofan isomeric mixture of tri(azidosulfonyl)-chlorooctadecyl azidoformates.A typical infrared spectrum of this product shows the strong azide bandat 2145 cm, the carbonyl band at 1735 cm., and sulfonyl peaks at 1165cm. and 1365 cm. A typical elemental analysis of the product is:

This product is useful as a cross-linking agent for polypropylene.

EXAMPLE 6 This example illustrates a process for making anazidosulfonylphenethyl azidoformate.

A solution of phenylethyl chloroformate (18.5 parts, 0.1 mole) inchloroform (90 parts) is cooled to 3C. and maintained at thistemperature while chlorosulfonic acid (23.2 parts, 0.2 mole) is addeddropwise. The resulting reaction mixture, typically a clear ambersolution, is stirred for 2 hours at 3C., and then gently refluxed (63C.)for 2 hours. Typically a dark heavy oil layer forms during therefluxing. After cooling to 20-25C., the reaction product is poured ontowet ice. Although there is a tendency for the thus cooled reactionmixture to emulsify, ultimately it separates into a water immisciblephase and a water phase. The water immiscible phase is separated fromthe aqueous phase, washed once with ice water, and dried over magnesiumsulfate. Chloroform is then stripped from the dried material to givetypically a slightly viscous colorless oil. A typical infrared spectrumof this oil shows the strong carbonyl peak at 1780 cm", and bands at1180 cm.

and 1380 emf, which are indicative of the desired sulfonyl chlorideradical.

A portion parts) of the oil is added to a slurry of sodium azide (6.6parts), water parts), methylene chloride (25 parts) and acetone (12parts). The mixture thus formed is stirred for 4 days at -25C. It isthen admixed with water (50 parts) and methylene chloride (30 parts).The result is a two-phase mixture. The water immiscible phase is removedfrom the mixture, washed with water and dried over magnesium sulfate.Methylene chloride and acetone are removed by vacuum (final pressure is1 millimeter of mercury) at 20 C. to give the desired product (3.5parts).

This product is typically a pale, yellow oil. It consists essentially ofan isomeric mixture of azidosulfonylphenethyl azidoformates, one ofwhich is pazidosulfonylphenethyl azidoformate. The infrared spectrum ofthis product typically has the desired azide doublet at 2140 cm. and2190 emf, a strong carbonyl band at 1740 cm. and the sulfonyl bands at1175 cm. and 1375 cm. A typical elemental anaylsis of the product is:

Analyzed Calculated EXAMPLE 7 This example illustrates a process formaking 4- azidosulfonylbicyclohexyl-4'-azidoformate.

From the corresponding hydroxysulfonic acid, 4-chlorosulfonylbicyclohexyl-4'-chloroformate is prepared as described inExample 1. To 2.8 parts of the 4-chlorosulfony1bicyclohexyl-4-chloroformate is added a slurry of sodiumazide (4 parts), water (6 parts) and acetone (35 parts). The mixturethus formed is stirred for 19 hours at room temperature. The product isrecovered by adding water (100 parts) to the reaction mixture and thenextracting the product with methylene chloride. The water-immisciblephase is separated from the aqueous phase, washed with water, dried oversodium sulfate, and then subjected to vacuum to remove substantially allof the methylene chloride. The resulting4-azidosu1fonylbicyc1ohexyl-4'-azidoformate displays a strong infraredspectrum peak at 2150 cm. as well as a carbonyl peak at 1750 cm. andsulfonyl peaks at 1375 cm. and 1165 cm.". The product was calculated tobe 94% pure based on the evolution of nitrogen gas at 165C.

This product is useful as a cross-linking agent.

EXAMPLE 8 This example illustrates the process for making 1-azidosulfonylphenyl-4-azidoformate.

The 1-chlorosulfonylphenyl-4-chloroformate is prepared fromphenylchloroformate as described in Example 6. To 22 parts of the1-chlorosulfonylphenyl-4- chloroformate in chloroform (100 parts) isadded a slurry of sodium azide (26 parts), water (50 parts) and acetone(30 parts). The reaction mixture is rapidly stirred and refluxed for 6hours. After cooling the organic layer is water washed and then driedover sodium sulfate. The chloroform is then removed by vacuum.

The 1-azidosulfonylphenyl-4-azidoformate shows normal infrared spectrumpeaks at 2140 cm. and 2190 cm. as well as a strong carbonyl peak at 1740cm".

A typical elemental analysis of the product is as fol- Percent Thisproduct is useful as a cross-linking agent.

EXAMPLE 9 This example illustrates the process for making 2-azidosulfonylnaphthalene-6-azidoformate.

The 2-chlorosulfonylnaphthalene-6-chloroformate is prepared from6-naphthol-2-sulfonic acid. To 4 parts of the2-chlorosulfonylnaphthalene-6-chloroformate in ethylene dichloride (100parts) is added a slurry of so dium azide (8 parts), water (20 parts)and acetone (30 parts). The mixture thus formed is rapidly stirred andrefluxed for 8 hours. After washing with water and drying over magnesiumsulfate the ethylene dichloride is removed by vacuum. The resulting 2-azidosulfonylnaphthalene-6-azidoformate exhibits a typical infraredspectrum with azide peaks at 2140 cm. and 2190 cm. and a strong carbonylpeak at 1740 cm.'.

This product is useful as a cross-linking agent.

EXAMPLE 10 This example illustrates the process for making 4-azidosulfonylbipheny1-4'-azidoformate.

A mixture of 3 parts of 4-chlorosu1fonylbiphenyl-4'- chloroformate(prepared from the corresponding hydroxysulfonic acid) parts of acetone,5 parts of sodium azide, and 10 parts of water is rapidly stirred atroom temperature for 19 hours. After washing with water and drying oversodium sulfate the product is recovered by removing the solvent undervacuum.

A typical elemental analysis of the 4-azidosulfonylbiphenyl-4-azidoformate product is as follows:

Analyzed, Percent 23.8 8.96 Calculated for C H N o S, 24.4 9.31

Percent This product is useful as a cross-linking agent.

EXAMPLE 11 The product is approximately 92% pure based on the evolutionof nitrogen gas at 160C.

This product is useful as a cross-linking agent.

EXAMPLE 12 This example illustrates the process for making an isomericmixture of azidosulfonyl-2-chlorocyclohexyl- 1 -azidoform ates.

A solution of 2-chlorocyclohexyl-1-chloroformate (20 parts) in methylenechloride (450 parts) is cooled at 5C. while passing in sulfur dioxidegas at a rate of 4.0 parts per hour. After about minutes the reactionmixture is exposed to ultraviolet light and chlorine gas is introducedinto the reaction mixture at a rate of 2.5 parts per hour. Both chlorineand sulfur dioxide are continuously added for 4 hours to the reactionmixture, and then their addition is stopped. The'methylene chloride isremoved by high vacuum from the reaction mixture, giving a mixture ofmonochlorosulfonyl-Z- chlorocyclohexyl-l-chloroformate isomers.

A portion (12 parts) of the monochlorosulfonyl-2-chlorocyclohexyl-l-chloroformate isomer mixture is added to acetone (90parts), water (10 parts) and sodium azide (8 parts). The mixture thusformed is stirred rapidly at room temperature for 6 hours, then dilutedwith 300 parts of water, washed with water and dried over sodiumsulfate. The resulting product consists essentially of4-azidosulfonyl-2-chlorocyclohexyl-lazidoformate and isomers of thiscompound.

A typical infrared spectrum of this product has a strong azide peak at2150 cm. and a carbonyl peak at 1740 cm.'.

A typical elemental analysis of this product is:

Analyzed, Percent 27.7 10.7 Calculated for C l-l ClN O,S, 27.2 10.3

Percent This product is useful as a cross-linking agent.

EXAMPLE 13 Analyzed, Percent 227 8.7 Calculated for C H N O,,S, 23.3 8.9

Percent This product is useful as a cross-linking agent.

EXAMPLE 14 This example illustrates the process for making 1-(4'-azidosulfonylphenylsulfonyl)phenyl-4-azidoformate.

A mixture of 2.8 parts of l-(4chlorosulfonylphenylsulfonyl)phenyl-4-chloroformate, acetone parts),water (10 parts) and sodium azide (2 parts) is stirred and refluxedunder nitrogen gas for 4 hours, then diluted with 150 parts of water.The resulting 1-(4-azidosulfonylphenylsulfonyl)phenyl-4- azidoformate isrecrystallized from warm alcohol.

A typical elemental analysis of this product is:

Analyzed, Percent Calculated for CHHBNQOBSD Percent This product isuseful as a cross-linking agent.

EXAMPLE 15 This example illustrates a process for the preparation of amixture of isomeric poly(azidosulfonyl)-dichlorotriacontane-30-azidoformates.

A solution of n-triacontanechloroformate (20 parts, prepared fromn-triacontanol and phosgene) in methylene chloride (200 parts) is cooledto 5C. Sulfur dioxide gas is then bubbled through the solution at a rateof about 7.2 parts per hour. After 15 minutes chlorine gas is introducedinto the reaction mixture at a rate of 3.9 parts per hour, and thereaction mixture is exposed to ultraviolet light. After approximately 10hours of reaction with both chlorine and sulfur dioxide bubbling intothe reaction mixture, the addition of both gases is stopped and theexposure of the reaction mixture to ultraviolet light is continued foran additional 2 hours. The resulting product is an isomeric mixture ofpoly(chlorosulfonyl)-dichlorotriacontane-30-chloroformate containing anaverage of 5 chlorosulfonyl groups and 2 chloro groups per molecule.

A portion (3.1 parts) of this intermediate product is admixed withacetone parts), water (15 parts) and sodium azide (9 parts) and stirredand refluxed for 5 hours. The resulting product is water washed, driedand then stripped of solvent to give poly(azidosulfonyl)-dichlorotriacontane-30-azidoformate containing an average of 5azidosulfonyl groups and 2 chloro groups per molecule.

A typical elemental analysis of the product is:

N S Cl Analyzed, Percent 224 14.7 6.8 Calaculated for c u o smupl 22.814.5 v 6.4

Percent This product is useful as a cross-linking agent.

EXAMPLE 16 in water (20 parts) and acetone (20 parts). The mixture thusformed is stirred rapidly and refluxed for 7 hours under an atmosphereof nitrogen. The reaction mixture is cooled, the organic layer washedwith water and then dried over magnesium sulfate. The solvent is removedunder vacuum yielding an isomeric mixture ofpoly(azidosulfonyl)-chlorotetradecane-1,l4-bis azidoformates containingan average of 2 azidosulfonyl groups and 1 chlorine group per molecule.An infrared spectrum of the product shows a strong azide peak at 2150cm. and a carbonyl peak at 1740 cm..

This product is useful as a cross-linking agent.

EXAMPLE 17 This example illustrates the use of the product of Example las a cross-linking agent for polyethylene.

A commercially available molding grade polyethylene (100 parts)containing 4,4'-thiobis(6-t-butyl-mcresol) (0.5 part) and calcium oxide(0.014 part) is milled on a two-roll mill at 280-290F. for 5 minutes. Aquantity (0.55 part) of the l-azidosulfonylpropyl-3- azidoformateproduct of Example 1 is added and the milling continued for 3 moreminutes. The polymer product that results is ankylomeric polyethylene.The polyethylene has reacted with a substantial portion of theazidoformate radicals in the Example 1 product, but the azidosulfonylradicals are substantially unreacted and the polymer product is not in asubstantially cured condition.

The ankylomeric polyethylene is then compression molded into a sheet orany other article of desired size and shape. To effect cure orcross-linking of this polymer product the sheet or article isestablished and maintained at 419F. for minutes. The thus treated sheetor article is characterized by increased solvent resistance and byincreased stress-crack resistance. It is also substantially odor free.

Instead of a milling and molding procedure, an extrusion procedure canbe employed. In such a procedure extrusion grade polyethylene (100parts) containing 4,4-thiobis(6-t-butyl-m-cresol) (0.5 part) and calciumoxide (0.014 part) and a quantity (0.55 part) of thelazidosulfonylpropyl-3-azidoformate product of Example 1 are extrudedtogether through an extruder at an extrusion temperature of about 330F.and with an extruder residence time of about 1 minute. A suitableextruder, for instance, is a V4 inch Braybender extruder employing a :1LB plastic extrusion screw with a 3:1 compression ratio. The extrudedpolymer product is ankylomeric polyethylene in that the polyethylene hasreacted with a substantial portion of the azidoformate radicals in theproduct of Example 1 without reaction of a substantial portion of theazidosulfonyl radicals. However, the polymer product is still soluble insubstantially the same solvents as the polyethylene before extrusion.The ankylomeric polyethylene in substantially uncured condition, whichcan be in the form of a rod or the like, is divided into particles suchas pellets, flakes and the like.

Thereafter, the extruded polymer product is either compression molded orextruded into any desired article. Curing of the polymer product in themolded or extruded article is effected by establishing and maintainingthe article for about 10-15 minutes at 419F. This can be done afterformation of the article, and it can be done during formation of thearticle as part of the molding or extrusion procedure. Upon cooling ofthe article to room temperature, the article typically has substantiallyincreased solvent resistance and substantially increased stress-crackresistance.

Instead of molding or extruding the polymer product into a shapedarticle, such can be applied as a curable coating to wire or a web. Thecure or cross-linking is effected, when the coating thickness is 30-50mils, by passing the coated wire or web at atmosphere pressure through a419F. oven with a residence time of about 10-15 minutes. When thecoating thickness is greater than about 50 mils and forming of thecoating is to be minimized, the cure or cross-linking is effected bypassing the coated wire or web through a pressurized enclosurecontaining saturated steam at about 400F. for about 4 minutes.

EXAMPLE 18 This example illustrates the use of the product of Example las a coupling agent in the bonding of polypropylene to ethylenicallyunsaturated organo silane treated glass.

Sheets of l81-style, E-glass cloth, 8.9 ounces per square yard, Finish112, pH neutral (heat cleaned), 8 sh satin weave (Hess Goldsmith &Company), are immersed in a water-solution of vinyl triacetoxysilane(1%), removed from the solution and then dried at a temperature of 23C.for 16 hours.

The thus treated cloth is immersed in a tetrachloroethylene solutioncontaining (at 0.14%) the 1- azidosulfonylpropyl-3-azidoformate productof Example 1, which solution is then established and maintained at atemperature of 121C. for l 96 hours. Typically about of the azidoformateradicals react with the treated glass cloth while about of theazidosulfonyl groups remain intact without decomposition or reaction.

The thus treated sheets of glass cloth are removed from theperchloroethylene solution and placed in a vacuum oven at 60C for 12hours to remove the perchloroethylene.

A 12 ply assembly of alternate plies of sheets of 5 mil thickpolypropylene and the thus treated sheets of glass cloth is formed. Theassembly is compression molded at a temperature of 220C. at a pressureof 250 pounds per square inch to a Iii inch thick laminate.

A test specimen 1 by 3 inch cut from the laminate and tested forflexural strength according to the American standard testing method D790in a 2 inch span at 0.5 inch/min. crosshead speed has a typical flexuralstrength of 2600 psi.

A test specimen 1 inch by 3 inch cut from a control laminate made asabove, except that treatment of the glass cloth with vinyltriacetoxysilane followed by the 1-azidosulfonylpropyl-3-azidoformateproduct of Example 1 is omitted, and tested for flexural strengthaccording to this test method has a typical flexural strength of 1400psi.

Hence, this invention provides a new and useful class of compounds. Inaddition it provides a new and useful class of polymers, namely,ankylomeric polymers.

Other features, advantages and specific'embodiments of this inventionwill become readily apparent to those in the exercise of ordinary skillin the art after reading the foregoing disclosures. These specificembodiments are within the scope of the claimed subject matter, unlessthe contrary is indicated. Moreover, while specific embodiments havebeen described in considerable detail, variations and modifications ofthese embodiments can be effected without departing from the spirit andscope of the invention as disclosed and claimed. What I claim and desireto protect by Letters Patent is:

1. A process which comprises: forming a blend of 1) at least one polymerselected from the group consisting of saturated, unsaturated, linear,non-linear, crystalline and amorphous hydrocarbon homopolymers,copolymers and terpolymers; cellulose esters; cellulose ethers;polyesters; poly(alkylene oxide) polymers; polyamides; condensationproducts of triallyl pentaerythritol and diallylidene pentaerythritol;esters of triallyl pentaerythritol and drying oil fatty acids;poly(vinyl alkyl ethers); poly(vinyl acetals); vinyl chloride polymershaving a vinyl chloride content of at least ten molpercent;'nitrocellulose; chlorinated natural rubber; sulfochlorinatedpolyethylene; polysulfide rubber; polyurethane rubber; poly(vinylacetate); ethylene-vinyl acetate copolymer; poly(vinylidene chloride);vinylidene chloride-acrylonitrile copolymers; ethyl acrylate-2-chloroethyl vinyl ether copolymers; poly(ethyl acrylate); poly(ethylmethacrylate); poly[3,'3-bis(- chloromethyl)oxetane]; vinyl modifiedpoly(dimethyl siloxane); polychloroprene; and butadieneacrylonitrilecopolymers; and (2) from about 0.01 to about 50% by weight based on theweight of the polymer of at least one azide compound having the formulawherein R is a polyvalent organic radical substantially inert to linkingreactions, n and m are each 1-10 and the ll ll -fiNa and OCN3 groups areattached to different carbon atoms in said R group; and establishing andmaintaining said blend at an elevated temperature range for a period oftime selected to effect reaction of a substantial portion of the groupsin said azide compounds with azidoformate and azidosulfonyl radicalreactive monomer units in said polymer.

2. A process according to claim I, wherein said blend is established andmaintained in a temperature range for a period of time selected toeffect combination reaction of a substantial portion of the groups inthe azide compound with azidoformate radical reactive monomer units inthe polymer material without effecting combination reaction of asubstantial portion of the group in said azide compound withazidosulfonyl radical reactive monomer units in said polymer material,whereby an ankylomeric polymer product is obtained; and subsequentlyestablishing and maintaining said ankylomeric polymer product in atemperature range for a period of time selected to effect combinationreaction of a substantial portion of the groups in said ankylomericpolymer product with azidosulfonyl radical reactive monomer units insaid ankylomeric polymer product.

3. A process for making an ankylomeric polymer product, which comprises:forming a blend of (l) at least one polymer selected from the groupconsisting of saturated, unsaturated, linear, non-linear, crystallineand amorphous hydrocarbon homopolymers, copolymers and terpolymers;cellulose esters; cellulose ethers; polyesters; poly(alkylene oxide)polymers; polyamides; condensation products of triallyl pentaerythritoland diallylidene pentaerythritol; esters of triallyl pentaerythritol anddrying oil fatty acids; poly(vinyl alkyl ethers); poly(vinyl acetals);vinyl chloride polymers having a vinyl chloride content of at least tenmol percent; nitrocellulose; chlorinated natural rubber;sulfochlorinated polyethylene; polysulfide rubber; polyurethane rubber;poly(vinyl acetate); ethylene-vinyl acetate copolymer; poly(vinylidenechloride); vinylidene chloride-acrylonitrile copolymers; ethylacrylate-2- chloroethyl vinyl ether copolymers; poly(ethyl acrylate);poly(ethyl methacrylate); poly[3,3-bis(- chloromethyl)oxetane]; vinylmodified poly(dimethyl siloxane); polychloroprene; andbutadieneacrylonitrile copolymers; and (2) from about 0.01 to about 50%by weight based on the weight of the polymer of at least one azidecompound having the formula Nita Git iv, m

wherein R is a polyvalent organic radical substantially inert to linkingreactions, n and m are each 1-10 and the groups are attached todifferent carbon atoms in said R group; and establishing and maintainingsaid blend at an elevated temperature range for a period of timeselected to effect reaction of a substantial portion of the li OCN:

group in said azide compound with azidosulfonyl radical reactive monomerunits in said polymer.

4. A process which comprises: establishing and maintaining anankylomeric polymer product atan elevated temperature range for a periodof time selected to effect reaction of a substantial portion of thegroups in said ankylomeric polymer product with azidosulfonyl radicalreactive monomer units in said ankylomeric polymer product, saidankylomeric polymer product being a polymer selected from the groupconsisting of saturated, unsaturated, linear, non-linear, crystallineand amorphous hydrocarbon homopo]y-. mers, copolymers and terpolymers;cellulose esters; cellulose ethers; polyesters; poly(alkylene oxide)polymers; polyamides; condensation products of triallyl pentaerythritoland diallylidene pentaerythritol; esters of triallyl pentaerythritol anddrying oil fatty acids; poly(vinyl alkyl ethers); poly(v ihyl acetals);vinyl chloride polymers having a vinyl chloride content of at least tenmol percent; nitrocellulose; chlorinated natural rubber;sulfochlorinated polyethylene; polysulfide rubber; polyurethane rubber;poly(vinyl acetate); ethylene-vinyl acetate copolymer; poly(vinylidenechloride); vinylidene chloride-acrylonitrile copolymers; ethylacrylate-Z-chloroethyl vinyl ether copolymers; poly(ethyl acrylate);poly( ethyl methacrylate); poly[3- ,3-bis(chloromethyl)oxetane]; vinylmodified poly(- dimethyl siloxane); polychloroprene; andbutadieneacrylonitrile copolymers, which has been modified by reactionwith at least one azide compound having the formula Mama wherein R is apolyvalent organic radical substantially inert to linking reactions, nand m are each 1-10 and the are attached to different carbon atoms insaid R group, under conditions such that the said azide compound hasbeen attached to the polymer through the groups leaving the groupssubstantially unreacted.

5. An ankylomeric polymer comprising a polymer selected from the groupconsisting of saturated, unsaturated, linear, non-linear, crystallineand amorphous hydrocarbon homopolymers, copolymers and terpolymers;cellulose esters; cellulose ethers; polyesters; poly- (alkylene oxide)polymers; polyamides; condensation products of triallyl pentaerythritoland diallylidene pentaerythritol; esters of triallyl pentaerythritol anddrying oil fatty acids; poly(vinyl alkyl ethers); poly(vinylacetals);-vinyl chloride polymers having a vinyl chloride content of atleast ten mol percent; nitrocellulose; chlorinated natural rubber;sulfochlorinated polyethylene; polysulfide rubber; polyurethane rubber;poly(vinyl acetate); ethylene-vinyl acetate copolymer; poly(vinylidenechloride); vinylidene chlorideacrylonitrile copolymers; ethylacrylate-Z-chloroethyl vinyl ether copolymers; poly(ethyl acrylate);poly(ethyl methacrylate); poly[3,3-bis(chloromethyl)oxetane]; vinylmodified poly(dimethyl siloxane); polychloroprene; andbutadiene-acrylonitrile copolymers, which has been modified by reactionwith at least one azide compound having the formula Nal lt oil a) allwherein R is a polyvalent organic radical substantially inert to linkingreactions, n and m are each 1-10 and the 0 ll ll T a and 0 ()Na groupsare attached to different carbon atoms in said R group, under conditionssuch that the said azide compound has been attached to the polymerthrough the groups leaving the groups substantially unreacted.

6. A polymer selected from the group consisting of saturated,unsaturated, linear, non-linear, crystalline and amorphous hydrocarbonhomopolymers, copolymers and terpolymers; cellulose esters; celluloseethers; polyesters; poly(alkylene oxide) polymers; polyamides;condensation products of triallyl pentaerythritol and diallylidenepentaerythritol; esters of triallyl pentearythritol and drying oil fattyacids; poly(vinyl alkyl ethers); poly(vinyl acetals); vinyl chloridepolymers having a vinyl chloride content of at least ten mol percent;nitrocellulose; chlorinated natural rubber; sulfochlorinatedpolyethylene; polysulfide rubber; polyurethane rubber; poly(vinylacetate); ethylene-vinyl acetate copolymer; poly(vinylidene chloride);vinylidene chloride-acrylonitrile copolymers; ethyl acrylate-2-chloroethyl vinyl ether copolymers; poly(ethyl acrylate); poly(ethylmethacrylate); poly[3,3-bis(- chloromethyl)oxetane]; vinyl modifiedpoly(dimethyl siloxane); polychloroprene; and butadieneacrylonitrilecopolymers cross-linked by reaction with at least one azide compoundhaving the formula wherein R is a polyvalent organic radicalsubstantially inert to linking reactions, n and m are each l-l and theII -I? a and 0 (3 Na groups are attached to different carbon atoms insaid R group.

7. A cross-linkable composition comprising a blend of (1) at least onepolymer selected from the group consisting of saturated, unsaturated,linear, non-linear, crystalline and amorphous hydrocarbon homopolymers,copolymers and terpolymers; cellulose esters; cellulose ethers;polyesters; poly(alkylene oxide) polymers; polyamides; condensationproducts of triallyl pentaerythritol and diallylidene pentaerythritol;esters of triallyl pentaerythritol and drying oil fatty acids;poly(vinyl alkyl ethers); poly(vinyl acetals); vinyl chloride polymershaving a vinyl chloride content of at least ten mol percent;nitrocellulose; chlorinated natural rubber; sulfochlorinatedpolyethylene; polysulfide rubber; polyurethane rubber; poly(vinylacetate); ethylene-vinyl acetate copolymer; poly(vinylidene chloride);vinylidene chloride-acrylonitrile copolymers; ethylacryIate-Z-chloroethyl vinyl ether copolymers; poly(ethyl acrylate);poly(ethyl methacrylate); Poly[3- ,3-bis(chloromethyl)oxetane1; vinylmodified poly(- dimethyl siloxane); polychloroprene; andbutadieneacrylonitrile copolymers; and (2) from about 0.01 to about 50%by weight based on the weight of the polymer of at least one azidecompound having the formula N ELR OFENa) wherein R is a polyvalentorganic radical substantially inert to linking reactions, n and m areeach 1-10 and the 1 o i 0 ll ll TEN; and OCN:i

groups are attached to different carbon atoms in said R group.

*gg gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,859,261 Dated January 7, 1975 Inventofls) David S., Bres1ow It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 7, line 26'of printed patent;

"34, should read -3,4-

Column 7, line 28 of printed patentf "azi'dosulfonylphanyl" should readazidosulfonylphenyl Column 11; line 8 of P inted patent? "5" should read--3-- Column 16, line 64 of printed patent; Insert -mixed-- after "is"Column 17, line 51 of printed patent;

Insert --hour after "one-half" Column 18, line 33 of printed patent;

"pastry" should read -pasty-- Column 24, line 61 of printed patenty'"11,14-bis" should read -l,l4-bis- Signed and sealed this 4th day ofMarch 1.975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents L AttestingOfficer and Trademarks J

2. A process according to cLaim 1, wherein said blend is established andmaintained in a temperature range for a period of time selected toeffect combination reaction of a substantial portion of the
 3. A processfor making an ankylomeric polymer product, which comprises: forming ablend of (1) at least one polymer selected from the group consisting ofsaturated, unsaturated, linear, non-linear, crystalline and amorphoushydrocarbon homopolymers, copolymers and terpolymers; cellulose esters;cellulose ethers; polyesters; poly(alkylene oxide) polymers; polyamides;condensation products of triallyl pentaerythritol and diallylidenepentaerythritol; esters of triallyl pentaerythritol and drying oil fattyacids; poly(vinyl alkyl ethers); poly(vinyl acetals); vinyl chloridepolymers having a vinyl chloride content of at least ten mol percent;nitrocellulose; chlorinated natural rubber; sulfochlorinatedpolyethylene; polysulfide rubber; polyurethane rubber; poly(vinylacetate); ethylene-vinyl acetate copolymer; poly(vinylidene chloride);vinylidene chloride-acrylonitrile copolymers; ethylacrylate-2-chloroethyl vinyl ether copolymers; poly(ethyl acrylate);poly(ethyl methacrylate); poly(3,3-bis(chloromethyl)oxetane); vinylmodified poly(dimethyl siloxane); polychloroprene; andbutadiene-acrylonitrile copolymers; and (2) from about 0.01 to about 50%by weight based on the weight of the polymer of at least one azidecompound having the formula
 4. A process which comprises: establishingand maintaining an ankylomeric polymer product at an elevatedtemperature range for a period of time selected to effect reaction of asubstantial portion of the
 5. An ankylomeric polymer comprising apolymer selected from the group consisting of saturated, unsaturated,linear, non-linear, crystalline and amorphous hydrocarbon homopolymers,copolymers and terpolymers; cellulose esters; cellulose ethers;polyesters; poly(alkylene oxide) polymers; polyamides; condensationproducts of triallyl pentaerythritol and diallylidene pentaerythritol;esters of triallyl pentaerythritol and drying oil fatty acids;poly(vinyl alkyl ethers); poly(vinyl acetals); vinyl chloride polymershaving a vinyl chloride content of at least ten mol percent;nitrocellulose; chlorinated natural rubber; sulfochlorinatedpolyethylene; polysulfide rubber; polyurethane rubber; poly(vinylacetate); ethylene-vinyl acetate copolymer; poly(vinylidene chloride);vinylidene chlorideacrylonitrile copolymers; ethylacrylate-2-chloroethyl vinyl ether copolymers; poly(ethyl acrylate);poly(ethyl methacrylate); poly(3,3-bis(chloromethyl)oxetane); vinylmodified poly(dimethyl siloxane); polychloroprene; andbutadiene-acrylonitrile copolymers, which has been modified by reactionwith at least one azide compound having the formula
 6. A polymerselected from the group consisting of saturated, unsaturated, linear,non-linear, crystalline and amorphous hydrocarbon homopolymers,copolymers and terpolymers; cellulose esters; cellulose ethers;polyesters; poly(alkylene oxide) polymers; polyamides; condensationproducts of triallyl pentaerythritol and diallylidene pentaerythritol;esters of triallyl pentearythritol and drying oil fatty acids;poly(vinyl alkyl ethers); poly(vinyl acetals); vinyl chloride polymershaving a vinyl chloride content of at least ten mol percent;nitrocellulose; chlorinated natural rubber; sulfochlorinatedpolyethylene; polysulfide rubber; polyurethane rubber; poly(vinylacetate); ethylene-vinyl acetate copolymer; poly(vinylidene chloride);vinylidene chloride-acrylonitrile copolymers; ethylacrylate-2-chloroethyl vinyl ether copolymers; poly(ethyl acrylate);poly(ethyl methacrylate); poly(3,3-bis(chloromethyl)oxetane); vinylmodified poly(dimethyl siloxane); polychloroprene; andbutadiene-acrylonitrile copolymers cross-linked by reaction with atleast one azide compound having the formula
 7. A CROSS-LINKABLECOMPOSITION COMPRISING A BLEND OF (1) AT LEAST ONE POLYMER SELECTED FROMTHE GROUP CONSISTING OF SATURATED, UNSATURATED, LINEAR, NON-LINEAR,CRYSTALLINE AND AMORPHOUS HYDROCARBON HOMOPOLYMERS, COPOLYMERS ANDTERPOLYMERS; CELLULOSE ESTERS; CELLULOSE ESTHERS; POLYESTERS;POLY(ALKYLENE OXIDE) POLYMERS; POLYAMIDES; CONDENSATION PRODUCTS OFTRIALLYL PENTAERYTHRITOL AND DIALLYLIDENE PENTAERYTHRITOL; ESTERS OFTRIALLYL PENTAERYTHRITOL AND DRYING OIL FATTY ACIDS; POLY(VINYL ALKYLETHERS); POLY(VINYL ACETALS); VINYL CHLORIDE POLYMERS HAVING A VINYLCHLORIDE CONTENT OF AT LEAST TEN MOL PERCENT; NITROCELLULOSE;CHLORINATED NATURAL RUBBER; SULFOCHLORINATED POLYETHYLENE; POLYSULFIDERUBBER; POLYURETHANE RUBBER; POLY(VINYL ACETATE); ETHYLENE-VINYL ACETATECOPOLYMER; POLY(VINYLIDENE CHLORIDE); VINYLIDENE CHLORIDE-ACRYLONITRILECOPOLYMERS; ETHYL ACRYLATE-2-CHLOROETHYL VINYL ETHER COPOLYMERS;POLY(ETHYL ACRYLATE); POLY(ETHYL METHACRYLATE);POLY(3,3-BIS(CHLOROMETHYL)OXETANE); VINYL MODIFIED POLY(DIMETHYLSILOXANE); POLYCHLOROPRENE; AND BUTADIENEACRYLONITRILE COPOLYMERS; AND(2) FROM ABOUT 0.01 TO ABOUT 50% BY WEIGHT BASED ON THE WEIGHT OF THEPOLYMER OF AT LEAST ONE AZIDE COMPOUND HAVING THE FORMULA